Dyestuffs of the anthraquinone series



Patented Sept. 3, 1940 DYESTUFFS OF THE ANTHRAQUINONE SERIES RichardFleischhauer, Frankfort-on-the-MainlFechenheim, Germany, assignor toGeneral Aniline & Film Corporation, a corporation of Delaware NoDrawing. Application November 16, 1938, Se-

rial No. 240,646. In Germany November 16,

l Claims.

bility of the new dyestuffs in water may be still further increased bytreating the dry dyestufis with sulfonating agents such as for examplesulfuric acid and chlorosulfonic acid and reprecip- H H; itating themfrom the solution in these sulfonat- 5 ing agents by the addition ofwater.

In order to further illustrate my invention the following examples aregiven, the parts being by weight and all temperatures in degrees 0NHROSOz-X Centigrade- 10 a Example 1 wherein R stands ror an aromaticradicle of the benzene series and X stands for a member se- Parts Of1-amino-4-b10m0ahthmqllin0n'9- lected from the group consisting ofaliphatic 2-su1f011ic acid are mixed W 16 parts of radicles and aromaticradicles of the benzene, amihophehol, 509 Parts Of Water, 5 Parts Ofnaphthalene and hydrogenated naphthalene se- 111m bicarbonate and alittle amount of pp i powder, and the mixture is stirred at about Thenew dyestuffs may be prepared for eX- 50-60 f0]? some hours, theCondensation ample by condensing l amino 4 halogenoan complete. Then thesolution is alkalized by the thraqujn ne 2 su1f nj acid with anaminoaddition of sodium carbonate, filtered while hot phenol Compoundand treating t 1 i 4 and from the filtrate the dyestuff formed is pre-20 hydroxyarylaminoanthraquinone-2-sulfonic acid Cipltated y theaddition of Sodium Chloridethus obtained with an aliphatic sulfochlorideor The intermediate dyeStU-ff thus Obtained is an aromatic sulfochlorideof the benzene, naphpurified, if necessary, by d ng it in Water thaleneor hydrogenated naphthalene series. and reprecipitating t from this lutn n Furthermore the manufacture of the new dyeit is again disfiolved inabout 1000 P ts O Wa- 25 stuffs may also be performed in anothersequence tel, and at about an excess of Otohlby combining aminophenolcompounds with 1. ene-S-sulfochloride is added. The mixture is ionicacid halides of the above said species and then stin'ed'for hours atabout with condensing the intermediate products thus 010- the additifmof Such an amount of Sodium tained withl-aminol-halogenoanthraquinonebonate Sodium hydroxide as ary for 3 2 1acid, keeping the solution always alkaline. When cool,

1 The new dyestuffs are distinguished from the the dyestllff formed ofthe formula? known l-amino-d-hydroxyphenylamino-anthra- 0 NHquinone-2-su1fonic acids which do not contain a H radicle of analiphatic or aromatic sulfonic acid -SO:Na 35 in theirhydroxyphenylamino group, by more reddish blue shades of the dyeingsobtained on CH3 wool and silk and by a considerably increased Y fastnessof these dyeings to Washing, fulling, sea- NH 3OSO2C CH Water andperspiration. Moreover those of the 1 40 new dyestuffs which contain theradicle of a is filtered oh and purified by washing or by dissubstitutedaromatic sulfonic acid in their molesolvingit in water andreprecipitating it from cule exhibit the valuable property of beingabthis solution. The new dyestuff is, when dry, a sorbed by animalfibers from a neutral bath with dark violet powder, soluble in water anddyeing an almost complete exhaustion of .the dyeing wool from a weaklyacid or neutral bath very 45 bath. fast reddish blue shades.

Most of the new dyestuffs possess, in spite of Similar dyestuffs oflikewise very good fasttheir great molecular weight, a good solubilityness properties are obtained by employing inin water, especially whenthey contain longstead of 3-chlorotoluene-6-suliochloride other chainaliphatic radicles. If necessary, the soluaromatic sulfochlorides of thebenzene, naph- 50 Example 2 43 parts of the sodium salt of the1-amino-4- (4 hydroxy phenylamino) anthraquinone-Z- sulfonic acid whichis prepared according to the first paragraph of Example 1, are dissolvedin water and treated at about 5060 with 17 parts ofchloroethanesulfochloride. When the reaction is complete, the solutionis filtered and from the filtrate the dyestuif formed of the formula:

NH: U I

is precipitated by the addition of sodium chloride. It is, when dry, aviolet-black powder, soluble in water and dyeing wool and silk blueshades of good fastness to perspiration and very good fastness to lightand seawater. The new dyestufi has a good levelling power.

Similar valuable dyestufis are obtained by employing instead ofch10roethanesulfochloride the corresponding amounts ofmethane-sulfochloride, ethanesulfochloride, propanesulfochloride orchloromethanesulfochloride.

Example 3 An aqueous solution of the sodium salt of the l-amino-l-(4'-hydroxyphenylamino) -anthraquinone-Z-sulfonic acid (preparedaccording to the first paragraph of Example 1) is treated with an excessof 2,4-diisopropylbenzenesulfochloride in an analogous manner asdescribed in Example 1. The new dyestuif thus obtained of the formula:

SOaNa is isolated and dried. It is a dark violet powder, soluble inwater and dyeing wool from a neutral bath reddish blue shades ofexcellent fastness properties.

Example 4 38.2 parts of 1-aminol-bromoanthraquinone- 2-sulfonic acid arecondensed in an. analogous manner as described in the first paragraph ofExample 1 with 18 parts of 1-amino-3-hydroxy- 6-methy1benzene at about60-70, advantageously with the addition of a little amount of alcohol.The intermediate dyestufi thus obtained is isolated, purified and thentreated with about 30 parts of -toluenesulfochloride at about 50-60 inan aqueous solution containing an excess of sodium carbonate. obtainedof the formula:

(I? NHz SOaNa which is, when dry, a violet-black powder. It is slightlysoluble in water and dyes wool navyblue shades of very good fastnessproperties.

Similar valuable dyestuifs are obtained by treating the condensationproducts of l-amino- 4-bromoanthraquinone-2-sulfonic acid and 2-aminophenol, 3-aminophenol or G-aminophenol- 2-carboxylic acid with4-toluenesulfochloride or similar sulfochloride compounds.

Example 5 32.2 parts of 1-amino-4-bromoanthraquinone- 2-sulfonic acidare mixed with about 1000 parts of water, 5 parts of sodium bicarbonate,26 parts of the benzenesulfonic acid ester of l-aminophenol, about 80parts of alcohol and a little amount of cuprous hydroxide, and themixture is heated to about 7080, until the condensation is almostcomplete. Then the dyestuff formed of the formula:

0 NHz ll I is precipitated and purified, if necessary, by dissolving itin water and reprecipitating it from this solution. It is, when dry, atviolet-black powder, soluble in water and dyeing wool from an acid bathblue shades of good fastness to perspiration and very good fastness toseawater.

Example 6 43 parts of the sodium salt of the l-amino-el- (4-hydroxyphenylamino) -anthraquinone-2-sulfonic acid (prepared accordingto the first paragraph of Example 1) are treated in an aqueous solutionat obout 50-60 with 27 parts of isohexyl-toluene-sulfochloride. The newdyestuif thus obtained of the formula:

SOaNa I aHn is isolated and dried. It is a dark violet pow der, solublein water and dyeing wool clear reddish blue shades of excellent fastnessto washing, fulling and perspiration and of good fastness to light.

Thereby a dyestuif is The isohexyl-to1uenesulfochloride employed for themanufacture of this dyestuif may be prepared for instance by acting withchlorosulfonic acid on isohexyltoluene which is obtained by condensingisohexylene with toluene in the presence of aluminium chloride. Hithertothe positions of the methyl, the isohexyl and the sulfochloride group inthe molecule of the isohexyl-toluenesulfochloride have not been foundout,.but probably the methyl and the isohexyl group stand in m-positionto each other.

Similar dyestufis which in part yield on wool somewhat more reddish blueshades are obtained by employing instead of isohexyltoluenesulfochlorideother sulfochloride compounds such as for example:

Isioctyl-toluenesulfochloride, 4-cycylohexylbenzenesulfochloride, 2,4-dicyclohexylbenzenesulfochloride, 2,4-diisohexylbenzene-sulfochloride, 2, 4-diisooctylbenzenesulfochloride,and the like.

Example 7 43 parts of the sodium salt of the l-aminol- (4hydroxyphenylamino) -anthraquinone-2-sulfonic acid (prepared accordingto the first paragraph of Example 1) are dissolved in water and treatedat about -90 with a mixture of aliphatic sulfochlorides with chains of12 to 20 carbon atoms. When the reaction is complete, the new dyestuifformed is isolated and dried. It is a dark powder, easily soluble inwater and dyeing wool from an acid bath very fast reddish blue shades.

By employing a mixture of aliphatic sulfochlorides with chains of 6 to'7 carbon atoms or other long-chain aliphatic sulfochlorides such as forexample decanesulfochloride similar valuable dyestuffs are obtained,dyeing wool somewhat brighter reddish blue shades of likewise very goodfastness properties.

I claim:

1. The dyestuifs of the anthraquinone series of the general formula:

(N) NE:

SOaH

SOxNa which dyestuif is a dark violet powder, soluble in water anddyeing wool very fast reddish blue shades.

3. The dyestuff of the formula:

S OaNa which dyestufi is a violet-black powder, soluble in water anddyeing wool and silk blue shades of good fastness properties.

4. The dyestuif of the formula:

-S OaNa which dyestuff is a dark violet powder soluble in water anddyeing wool reddish blue shades of excellent fastness properties.

RICHARD FLEISCI-II-IAUER.

